Macroporous titanium tetraphosphonate materials with intraframework ethylenediamine groups and hierarchical rneso-structure in the walls were synthesized by a simple surfactant-free process with the use of sodium salt of ethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid), possessing large capacity for heavy metal ion adsorption with a preference sequence of Cd2+ < Cu2+ < Pb2+.